9-Benzyl-10-methyl­acridinium trifluoro­methane­sulfonate

Trzybiński, D.; Zadykowicz, B.; Krzymiński, K.; Sikorski, A.; Błażejowski, J.

doi:10.1107/S160053681001963X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 7| July 2010| Pages o1548-o1549

doi:10.1107/S160053681001963X

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9-Benzyl-10-methylacridinium trifluoromethanesulfonate

Damian Trzybiński,^a Beata Zadykowicz,^a Karol Krzymiński,^a Artur Sikorski ^a and Jerzy Błażejowski ^a ^*

^aFaculty of Chemistry, University of Gdańsk, J. Sobieskiego 18, 80-952 Gdańsk, Poland
^*Correspondence e-mail: bla@chem.univ.gda.pl

(Received 18 May 2010; accepted 25 May 2010; online 5 June 2010)

In the crystal structure of the title compound, C₂₁H₁₈N⁺·CF₃OS₃⁻, the cations form inversion dimers through π–π interactions between the acridine ring systems. These dimers are further linked by C—H⋯π interactions. The cations and anions are connected by C—H⋯O, C—F⋯π and S—O⋯π interactions. The acridine and benzene ring systems are oriented at a dihedral angle of 76.8 (1)°with respect to each other. The acridine moieties are either parallel or inclined at an angle of 62.4 (1)° in the crystal structure.

Related literature

For general background to acridinium derivatives, see: King et al. (2007 ); Roda et al. (2003 ); Wróblewska et al. (2004 ); Trzybiński et al. (2010 ); Zomer & Jacquemijns (2001 ). For related structures, see: Sikorski et al. (2007 ); Trzybiński et al. (2010). For intermolecular interactions, see: Bianchi et al. (2004 ); Dorn et al. (2005 ); Hunter et al. (2001 ); Novoa et al. (2006 ); Takahashi et al. (2001 ). For the synthesis, see: Huntress & Shaw (1948 ); Sikorski et al. (2007); Trzybiński et al. (2010).

Experimental

Crystal data

C₂₁H₁₈N⁺·CF₃O₃S⁻
M_r = 433.44
Monoclinic, P 2₁ /n
a = 14.6211 (7) Å
b = 8.2514 (2) Å
c = 17.2900 (8) Å
β = 107.707 (5)°
V = 1987.12 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 295 K
0.41 × 0.25 × 0.08 mm

Data collection

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ) T_min = 0.953, T_max = 0.988
16520 measured reflections
3528 independent reflections
2191 reflections with I > 2σ(I)
R_int = 0.048

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.153
S = 1.06
3528 reflections
272 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg4 is the centroid of the C16–C21 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯O26ⁱ	0.93	2.49	3.398 (5)	167
C3—H3⋯Cg4ⁱⁱ	0.93	2.74	3.630 (5)	161
C15—H15B⋯O25ⁱⁱⁱ	0.97	2.49	3.423 (4)	160
C22—H22B⋯O25^iv	0.96	2.56	3.386 (5)	144
C22—H22C⋯O24	0.96	2.56	3.361 (5)	141
Symmetry codes: (i) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (ii) -x+2, -y, -z+1; (iii) -x+2, -y+1, -z+1; (iv) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 2
C–F⋯π and S–O⋯π interactions (Å,°)

Cg1 and Cg3 are the centroids of the C9/N10/C11–C14 and C5–C8/C13/C14 rings, respectively.

X	I	J	I⋯J	X⋯J	X–I⋯J
C27	F30	Cg3^v	3.115 (3)	4.233 (3)	143.0 (2)
S23	O26	Cg1^v	3.085 (3)	4.167 (2)	131.4 (2)
Symmetry code: (v) –x + $[{3\over 2}]$ , y + $[{1\over 2}]$ , –z + $[{1\over 2}]$ .

Table 3
π–π interactions (Å, °)

Cg1 and Cg2 are the centroids of the C9/N10/C11–C14 and C1–C4/C11/C12 rings, respectively. CgI⋯CgJ is the distance between ring centroids. The dihedral angle is that between the planes of the rings I and J. CgI_Perp is the perpendicular distance of CgI from ring J. CgI_Offset is the distance between CgI and perpendicular projection of CgJ on ring I.

I	J	CgI⋯CgJ	Dihedral angle	CgI_Perp	CgI_Offset
1	2ⁱⁱⁱ	3.806 (2)	2.11 (15)	3.575 (2)	1.306 (2)
2	1ⁱⁱⁱ	3.806 (2)	2.11 (15)	3.530 (2)	1.423 (2)
2	2ⁱⁱⁱ	3.886 (2)	0.02 (15)	3.563 (2)	1.551 (2)
Symmetry code: (iii) –x + 2, –y + 1, –z + 1.

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England.]$ ); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997 ); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681001963X/om2343sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681001963X/om2343Isup2.hkl

checkCIF report

Comment top

Quaternary N-methylacridinium cations substituted in position 9 undergo oxidation with H₂O₂ or other oxidants in alkaline media accompanied by chemiluminescence (Zomer & Jacquemijns, 2001). The emission that originates from electronically excited 10-methyl-9-acridinone, the oxidation product, is affected by the features of the substituent in position 9. For these reasons various acridine derivatives of the above type have been synthesized and investigated from the point of view of their chemiluminogenic ability and applicability in immunological, biological, chemical and environmental analyses (Zomer & Jacquemijns, 2001; Roda et al., 2003; King et al., 2007). Continuing the search for 9-substituted acridinium derivatives with chemiluminogenic potential (Wróblewska et al., 2004; Trzybiński et al., 2010), we synthesized 9-benzyl-10-methylacridinium trifluoromethanesulfonate whose crystal structure is presented here.

In the crystal structure, the inversely oriented cations form dimers through multidirectional π–π interactions involving acridine moieties (Table 3, Fig. 2). These dimers are linked by C–H···O (Table 1, Figs. 1 and 2), C–F···π (acridine) (Table 2, Fig. 2) and S–O···π (acridine) (Table 2, Fig. 2) interactions with adjacent anions, and by C–H···π (phenyl) (Table 1, Fig. 2) interactions with neighboring cations. The C–H···O interactions are of the hydrogen bond type (Bianchi et al., 2004; Novoa et al., 2006). The C–H···π interactions should be of an attractive nature (Takahashi et al., 2001), like the C–F···π (Dorn et al., 2005), S–O···π (Dorn et al., 2005) and the π–π (Hunter et al., 2001) interactions. The crystal structure is stabilized by a network of these short-range specific interactions and by long-range electrostatic interactions between ions.

In the cation of the title compound (Fig. 1), the bond lengths and angles characterizing the geometry of the acridinium moiety are typical of acridine-based derivatives (Sikorski et al., 2007; Trzybiński et al., 2010). With respective average deviations from planarity of 0.0427 (3) Å and 0.0066 (3) Å, the acridine and benzene ring systems are oriented at 76.8 (1)°. The acridine moieties in pairs are parallel (remain at an angle of 0.0 (1)°), while in adjacent pairs they are inclined at an angle of 62.4 (1)°. The mutual arrangement of the acridine and benzene ring systems, as well as the acridine skeletons in the crystal lattice is similar in the compound investigated and its precursor – 9-benzylacridine (Sikorski et al., 2007).

Related literature top

For general background to acridinium derivatives, see: King et al. (2007); Roda et al. (2003); Wróblewska et al. (2004); Trzybiński et al. (2010); Zomer & Jacquemijns (2001). For related structures, see: Sikorski et al. (2007); Trzybiński et al. (2010). For intermolecular interactions, see: Bianchi et al. (2004); Dorn et al. (2005); Hunter et al. (2001); Novoa et al. (2006); Takahashi et al. (2001). For the synthesis, see: Huntress & Shaw (1948); Sikorski et al. (2007); Trzybiński et al. (2010).

Experimental top

9-Benzylacridine was prepared by treating N-phenylaniline with an equimolar amount of phenylacetic acid, both dispersed in molten zinc chloride (Huntress & Shaw, 1948; Sikorski et al., 2007). The crude product was purified chromatographically (SiO₂, cyclohexane-ethyl acetate, 5:2 v/v). The compound thus obtained was quaternarized with a five-fold molar excess of methyltrifluoromethanesulfonate dissolved in anhydrous dichloromethane (Trzybiński et al., 2010). The crude 9-benzyl-10-methylacridinium trifluoromethanesulfonate was dissolved in a small amount of ethanol, filtered, and precipitated with a 25 v/v excess of diethyl ether. Light-orange crystals suitable for X-Ray investigations were grown from absolute ethanol solution (m.p. 478–480 K).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell refinement: CrysAlis RED (Oxford Diffraction, 2008); data reduction: CrysAlis RED (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

Fig. 1. The molecular structure of the title compound showing the atom-labeling scheme. Displacement ellipsoids are drawn at the 25% probability level and H atoms are shown as small spheres of arbitrary radius. Cg1, Cg2, Cg3 and Cg4 denote the ring centroids. The C–H···O hydrogen bond is represented by a dashed line.

Fig. 2. The arrangement of the ions in the crystal structure. The C–H···O interactions are represented by dashed lines, the C–H···π, C–F···π, S–O···π and π–π contacts by dotted lines. H atoms not involved in interactions have been omitted. [Symmetry codes: (i) x + 1/2, –y + 1/2, z + 1/2; (ii) –x + 2, –y, –z + 1; (iii) –x + 2, –y + 1, –z + 1; (iv) –x + 3/2, y – 1/2, –z + 1/2; (v) –x + 3/2, y + 1/2, –z + 1/2.]

9-Benzyl-10-methylacridinium trifluoromethanesulfonate top

Crystal data top

C₂₁H₁₈N⁺·CF₃O₃S⁻	F(000) = 896
M_r = 433.44	D_x = 1.449 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5587 reflections
a = 14.6211 (7) Å	θ = 3.2–29.2°
b = 8.2514 (2) Å	µ = 0.22 mm⁻¹
c = 17.2900 (8) Å	T = 295 K
β = 107.707 (5)°	Plate, light-orange
V = 1987.12 (15) Å³	0.41 × 0.25 × 0.08 mm
Z = 4

Data collection top

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer	3528 independent reflections
Radiation source: Enhanced (Mo) X-ray Source	2191 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.048
Detector resolution: 10.4002 pixels mm^-1	θ_max = 25.1°, θ_min = 3.3°
ω scans	h = −17→12
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	k = −9→9
T_min = 0.953, T_max = 0.988	l = −20→20
16520 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.153	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0814P)² + 0.218P] where P = (F_o² + 2F_c²)/3
3528 reflections	(Δ/σ)_max = 0.001
272 parameters	Δρ_max = 0.37 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

C₂₁H₁₈N⁺·CF₃O₃S⁻	V = 1987.12 (15) Å³
M_r = 433.44	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 14.6211 (7) Å	µ = 0.22 mm⁻¹
b = 8.2514 (2) Å	T = 295 K
c = 17.2900 (8) Å	0.41 × 0.25 × 0.08 mm
β = 107.707 (5)°

Data collection top

Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer	3528 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008)	2191 reflections with I > 2σ(I)
T_min = 0.953, T_max = 0.988	R_int = 0.048
16520 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.153	H-atom parameters constrained
S = 1.06	Δρ_max = 0.37 e Å⁻³
3528 reflections	Δρ_min = −0.28 e Å⁻³
272 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	1.0142 (2)	0.2164 (4)	0.5705 (2)	0.0680 (10)
H1	1.0341	0.1838	0.6245	0.082*
C2	1.0692 (3)	0.1812 (4)	0.5215 (3)	0.0870 (13)
H2	1.1267	0.1251	0.5419	0.104*
C3	1.0384 (4)	0.2302 (5)	0.4410 (3)	0.0919 (14)
H3	1.0760	0.2037	0.4081	0.110*
C4	0.9568 (3)	0.3141 (4)	0.4080 (3)	0.0793 (11)
H4	0.9395	0.3451	0.3538	0.095*
C5	0.6717 (3)	0.5685 (3)	0.4389 (2)	0.0616 (9)
H5	0.6566	0.6103	0.3866	0.074*
C6	0.6130 (3)	0.5955 (4)	0.4840 (3)	0.0703 (10)
H6	0.5572	0.6554	0.4620	0.084*
C7	0.6331 (2)	0.5369 (4)	0.5617 (2)	0.0641 (9)
H7	0.5903	0.5551	0.5911	0.077*
C8	0.7146 (2)	0.4531 (3)	0.59546 (18)	0.0515 (8)
H8	0.7275	0.4155	0.6484	0.062*
C9	0.8675 (2)	0.3374 (3)	0.58718 (16)	0.0416 (7)
N10	0.8163 (2)	0.4426 (3)	0.42625 (14)	0.0545 (7)
C11	0.9266 (2)	0.3027 (3)	0.53895 (18)	0.0490 (8)
C12	0.8982 (2)	0.3545 (3)	0.45600 (19)	0.0536 (8)
C13	0.7815 (2)	0.4203 (3)	0.55233 (15)	0.0411 (7)
C14	0.7575 (2)	0.4760 (3)	0.47112 (18)	0.0486 (8)
C15	0.8974 (2)	0.2879 (3)	0.67532 (17)	0.0514 (8)
H15A	0.8641	0.3559	0.7039	0.062*
H15B	0.9657	0.3076	0.6987	0.062*
C16	0.8769 (2)	0.1104 (3)	0.68912 (16)	0.0450 (7)
C17	0.7896 (2)	0.0396 (3)	0.64921 (19)	0.0565 (8)
H17	0.7431	0.0991	0.6111	0.068*
C18	0.7708 (2)	−0.1185 (4)	0.6653 (2)	0.0623 (9)
H18	0.7117	−0.1645	0.6383	0.075*
C19	0.8388 (3)	−0.2080 (4)	0.72059 (19)	0.0661 (10)
H19	0.8256	−0.3141	0.7320	0.079*
C20	0.9259 (3)	−0.1408 (4)	0.7590 (2)	0.0739 (11)
H20	0.9730	−0.2022	0.7954	0.089*
C21	0.9445 (3)	0.0179 (4)	0.74392 (18)	0.0627 (9)
H21	1.0038	0.0631	0.7713	0.075*
C22	0.7881 (3)	0.4991 (6)	0.3401 (2)	0.0921 (13)
H22A	0.7789	0.6144	0.3383	0.138*
H22B	0.7294	0.4470	0.3098	0.138*
H22C	0.8379	0.4721	0.3167	0.138*
S23	0.84575 (6)	0.55745 (8)	0.14455 (5)	0.0509 (3)
O24	0.8608 (2)	0.4008 (3)	0.17948 (15)	0.0869 (8)
O25	0.87049 (18)	0.6881 (3)	0.20097 (14)	0.0771 (7)
O26	0.75711 (18)	0.5802 (3)	0.08205 (16)	0.0925 (8)
C27	0.9326 (2)	0.5715 (3)	0.09040 (19)	0.0553 (8)
F28	1.01928 (18)	0.5412 (4)	0.13525 (16)	0.1322 (11)
F29	0.9156 (2)	0.4660 (3)	0.03015 (15)	0.1090 (9)
F30	0.9335 (2)	0.7119 (3)	0.05685 (18)	0.1184 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.051 (2)	0.0523 (17)	0.102 (3)	−0.0032 (16)	0.025 (2)	−0.0051 (18)
C2	0.062 (3)	0.061 (2)	0.147 (4)	−0.0002 (18)	0.045 (3)	−0.014 (3)
C3	0.098 (4)	0.074 (3)	0.133 (4)	−0.020 (2)	0.078 (3)	−0.035 (3)
C4	0.094 (3)	0.070 (2)	0.092 (3)	−0.021 (2)	0.055 (3)	−0.021 (2)
C5	0.063 (2)	0.0494 (17)	0.058 (2)	−0.0072 (16)	−0.0032 (18)	0.0132 (15)
C6	0.058 (2)	0.0511 (18)	0.092 (3)	0.0070 (16)	0.007 (2)	−0.0005 (19)
C7	0.055 (2)	0.0556 (18)	0.082 (3)	0.0044 (16)	0.0208 (19)	−0.0152 (18)
C8	0.057 (2)	0.0479 (16)	0.0494 (17)	−0.0042 (15)	0.0155 (16)	−0.0066 (13)
C9	0.0406 (17)	0.0361 (14)	0.0437 (16)	−0.0092 (12)	0.0063 (14)	−0.0046 (12)
N10	0.0601 (18)	0.0573 (14)	0.0459 (14)	−0.0176 (13)	0.0158 (13)	0.0010 (12)
C11	0.0440 (18)	0.0397 (14)	0.065 (2)	−0.0079 (13)	0.0191 (16)	−0.0050 (14)
C12	0.061 (2)	0.0460 (16)	0.064 (2)	−0.0236 (15)	0.0350 (18)	−0.0155 (15)
C13	0.0463 (17)	0.0345 (13)	0.0397 (15)	−0.0065 (12)	0.0091 (13)	−0.0031 (12)
C14	0.054 (2)	0.0409 (15)	0.0485 (18)	−0.0132 (13)	0.0121 (16)	0.0005 (13)
C15	0.0536 (19)	0.0475 (16)	0.0480 (17)	−0.0013 (13)	0.0078 (15)	0.0024 (13)
C16	0.0483 (18)	0.0450 (15)	0.0387 (15)	−0.0019 (13)	0.0088 (14)	−0.0037 (12)
C17	0.0489 (19)	0.0520 (17)	0.0626 (19)	−0.0003 (14)	0.0081 (16)	−0.0030 (15)
C18	0.061 (2)	0.0570 (19)	0.069 (2)	−0.0097 (16)	0.0209 (18)	−0.0068 (17)
C19	0.101 (3)	0.0482 (17)	0.055 (2)	−0.0102 (19)	0.032 (2)	−0.0009 (16)
C20	0.095 (3)	0.058 (2)	0.053 (2)	0.004 (2)	−0.0001 (19)	0.0128 (16)
C21	0.068 (2)	0.0598 (19)	0.0486 (18)	−0.0066 (16)	0.0000 (17)	0.0059 (15)
C22	0.095 (3)	0.134 (3)	0.046 (2)	−0.025 (3)	0.020 (2)	0.017 (2)
S23	0.0509 (5)	0.0466 (4)	0.0560 (5)	−0.0018 (3)	0.0174 (4)	−0.0017 (3)
O24	0.131 (2)	0.0614 (14)	0.0900 (17)	0.0137 (14)	0.0658 (17)	0.0192 (13)
O25	0.0813 (18)	0.0706 (14)	0.0855 (16)	−0.0086 (12)	0.0343 (14)	−0.0294 (13)
O26	0.0492 (15)	0.114 (2)	0.1010 (19)	−0.0060 (14)	0.0025 (14)	−0.0007 (16)
C27	0.058 (2)	0.0492 (17)	0.060 (2)	0.0005 (15)	0.0213 (17)	0.0023 (15)
F28	0.0559 (15)	0.234 (3)	0.1091 (19)	0.0300 (17)	0.0292 (14)	0.015 (2)
F29	0.159 (3)	0.0953 (15)	0.1012 (17)	−0.0266 (15)	0.0826 (17)	−0.0321 (13)
F30	0.156 (2)	0.0668 (13)	0.172 (2)	0.0008 (14)	0.108 (2)	0.0329 (14)

Geometric parameters (Å, º) top

C1—C2	1.364 (5)	C13—C14	1.416 (4)
C1—C11	1.421 (4)	C15—C16	1.528 (4)
C1—H1	0.9300	C15—H15A	0.9700
C2—C3	1.387 (6)	C15—H15B	0.9700
C2—H2	0.9300	C16—C21	1.374 (4)
C3—C4	1.346 (6)	C16—C17	1.382 (4)
C3—H3	0.9300	C17—C18	1.378 (4)
C4—C12	1.403 (5)	C17—H17	0.9300
C4—H4	0.9300	C18—C19	1.367 (4)
C5—C6	1.342 (5)	C18—H18	0.9300
C5—C14	1.428 (4)	C19—C20	1.363 (5)
C5—H5	0.9300	C19—H19	0.9300
C6—C7	1.372 (5)	C20—C21	1.378 (4)
C6—H6	0.9300	C20—H20	0.9300
C7—C8	1.348 (4)	C21—H21	0.9300
C7—H7	0.9300	C22—H22A	0.9600
C8—C13	1.425 (4)	C22—H22B	0.9600
C8—H8	0.9300	C22—H22C	0.9600
C9—C13	1.396 (4)	S23—O24	1.415 (2)
C9—C11	1.402 (4)	S23—O25	1.425 (2)
C9—C15	1.508 (4)	S23—O26	1.425 (2)
N10—C14	1.350 (4)	S23—C27	1.796 (3)
N10—C12	1.361 (4)	C27—F28	1.293 (4)
N10—C22	1.495 (4)	C27—F30	1.297 (3)
C11—C12	1.432 (4)	C27—F29	1.322 (3)

C2—C1—C11	120.1 (4)	C9—C15—C16	114.0 (2)
C2—C1—H1	120.0	C9—C15—H15A	108.8
C11—C1—H1	120.0	C16—C15—H15A	108.8
C1—C2—C3	119.2 (4)	C9—C15—H15B	108.8
C1—C2—H2	120.4	C16—C15—H15B	108.8
C3—C2—H2	120.4	H15A—C15—H15B	107.7
C4—C3—C2	123.4 (4)	C21—C16—C17	118.1 (3)
C4—C3—H3	118.3	C21—C16—C15	120.4 (3)
C2—C3—H3	118.3	C17—C16—C15	121.5 (2)
C3—C4—C12	119.6 (4)	C18—C17—C16	120.6 (3)
C3—C4—H4	120.2	C18—C17—H17	119.7
C12—C4—H4	120.2	C16—C17—H17	119.7
C6—C5—C14	120.2 (3)	C19—C18—C17	120.4 (3)
C6—C5—H5	119.9	C19—C18—H18	119.8
C14—C5—H5	119.9	C17—C18—H18	119.8
C5—C6—C7	121.7 (3)	C20—C19—C18	119.6 (3)
C5—C6—H6	119.2	C20—C19—H19	120.2
C7—C6—H6	119.2	C18—C19—H19	120.2
C8—C7—C6	120.2 (4)	C19—C20—C21	120.3 (3)
C8—C7—H7	119.9	C19—C20—H20	119.9
C6—C7—H7	119.9	C21—C20—H20	119.9
C7—C8—C13	121.9 (3)	C16—C21—C20	121.1 (3)
C7—C8—H8	119.1	C16—C21—H21	119.5
C13—C8—H8	119.1	C20—C21—H21	119.5
C13—C9—C11	118.7 (3)	N10—C22—H22A	109.5
C13—C9—C15	121.0 (3)	N10—C22—H22B	109.5
C11—C9—C15	120.2 (3)	H22A—C22—H22B	109.5
C14—N10—C12	122.2 (3)	N10—C22—H22C	109.5
C14—N10—C22	118.6 (3)	H22A—C22—H22C	109.5
C12—N10—C22	119.2 (3)	H22B—C22—H22C	109.5
C9—C11—C1	121.4 (3)	O24—S23—O25	115.13 (15)
C9—C11—C12	119.4 (3)	O24—S23—O26	115.57 (17)
C1—C11—C12	119.2 (3)	O25—S23—O26	113.74 (15)
N10—C12—C4	122.0 (3)	O24—S23—C27	103.79 (14)
N10—C12—C11	119.5 (3)	O25—S23—C27	103.62 (15)
C4—C12—C11	118.5 (3)	O26—S23—C27	102.73 (16)
C9—C13—C14	120.4 (3)	F28—C27—F30	107.4 (3)
C9—C13—C8	122.6 (2)	F28—C27—F29	105.1 (3)
C14—C13—C8	117.0 (3)	F30—C27—F29	105.1 (3)
N10—C14—C13	119.6 (3)	F28—C27—S23	113.2 (2)
N10—C14—C5	121.5 (3)	F30—C27—S23	113.3 (2)
C13—C14—C5	118.9 (3)	F29—C27—S23	112.0 (2)

C11—C1—C2—C3	−0.2 (5)	C12—N10—C14—C5	−179.9 (2)
C1—C2—C3—C4	1.2 (6)	C22—N10—C14—C5	−2.4 (4)
C2—C3—C4—C12	−0.6 (6)	C9—C13—C14—N10	2.8 (4)
C14—C5—C6—C7	0.4 (5)	C8—C13—C14—N10	−177.3 (2)
C5—C6—C7—C8	1.6 (5)	C9—C13—C14—C5	−176.4 (2)
C6—C7—C8—C13	−0.9 (4)	C8—C13—C14—C5	3.5 (4)
C13—C9—C11—C1	−179.0 (2)	C6—C5—C14—N10	177.8 (3)
C15—C9—C11—C1	2.0 (4)	C6—C5—C14—C13	−3.0 (4)
C13—C9—C11—C12	0.7 (4)	C13—C9—C15—C16	99.8 (3)
C15—C9—C11—C12	−178.3 (2)	C11—C9—C15—C16	−81.1 (3)
C2—C1—C11—C9	178.5 (3)	C9—C15—C16—C21	136.1 (3)
C2—C1—C11—C12	−1.2 (4)	C9—C15—C16—C17	−45.8 (4)
C14—N10—C12—C4	177.2 (3)	C21—C16—C17—C18	1.1 (5)
C22—N10—C12—C4	−0.4 (4)	C15—C16—C17—C18	−177.0 (3)
C14—N10—C12—C11	−3.7 (4)	C16—C17—C18—C19	−0.5 (5)
C22—N10—C12—C11	178.8 (3)	C17—C18—C19—C20	−1.0 (5)
C3—C4—C12—N10	178.3 (3)	C18—C19—C20—C21	1.9 (5)
C3—C4—C12—C11	−0.9 (5)	C17—C16—C21—C20	−0.2 (5)
C9—C11—C12—N10	2.8 (4)	C15—C16—C21—C20	177.9 (3)
C1—C11—C12—N10	−177.5 (2)	C19—C20—C21—C16	−1.3 (5)
C9—C11—C12—C4	−178.0 (3)	O24—S23—C27—F28	−54.1 (3)
C1—C11—C12—C4	1.7 (4)	O25—S23—C27—F28	66.5 (3)
C11—C9—C13—C14	−3.5 (4)	O26—S23—C27—F28	−174.8 (3)
C15—C9—C13—C14	175.5 (2)	O24—S23—C27—F30	−176.8 (3)
C11—C9—C13—C8	176.6 (2)	O25—S23—C27—F30	−56.1 (3)
C15—C9—C13—C8	−4.4 (4)	O26—S23—C27—F30	62.5 (3)
C7—C8—C13—C9	178.3 (2)	O24—S23—C27—F29	64.6 (3)
C7—C8—C13—C14	−1.7 (4)	O25—S23—C27—F29	−174.8 (2)
C12—N10—C14—C13	0.9 (4)	O26—S23—C27—F29	−56.2 (2)
C22—N10—C14—C13	178.5 (3)

Hydrogen-bond geometry (Å, º) top

Cg4 is the centroid of the C16–C21 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O26ⁱ	0.93	2.49	3.398 (5)	167
C3—H3···Cg4ⁱⁱ	0.93	2.74	3.630 (5)	161
C15—H15B···O25ⁱⁱⁱ	0.97	2.49	3.423 (4)	160
C22—H22B···O25^iv	0.96	2.56	3.386 (5)	144
C22—H22C···O24	0.96	2.56	3.361 (5)	141

Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+2, −y, −z+1; (iii) −x+2, −y+1, −z+1; (iv) −x+3/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₂₁H₁₈N⁺·CF₃O₃S⁻
M_r	433.44
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	295
a, b, c (Å)	14.6211 (7), 8.2514 (2), 17.2900 (8)
β (°)	107.707 (5)
V (Å³)	1987.12 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.41 × 0.25 × 0.08

Data collection
Diffractometer	Oxford Diffraction Gemini R Ultra Ruby CCD diffractometer
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.953, 0.988
No. of measured, independent and observed [I > 2σ(I)] reflections	16520, 3528, 2191
R_int	0.048
(sin θ/λ)_max (Å⁻¹)	0.597

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.153, 1.06
No. of reflections	3528
No. of parameters	272
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.37, −0.28

Computer programs: CrysAlis CCD (Oxford Diffraction, 2008), CrysAlis RED (Oxford Diffraction, 2008), SHELXS97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

Cg4 is the centroid of the C16–C21 ring.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···O26ⁱ	0.93	2.49	3.398 (5)	167
C3—H3···Cg4ⁱⁱ	0.93	2.74	3.630 (5)	161
C15—H15B···O25ⁱⁱⁱ	0.97	2.49	3.423 (4)	160
C22—H22B···O25^iv	0.96	2.56	3.386 (5)	144
C22—H22C···O24	0.96	2.56	3.361 (5)	141

Symmetry codes: (i) x+1/2, −y+1/2, z+1/2; (ii) −x+2, −y, −z+1; (iii) −x+2, −y+1, −z+1; (iv) −x+3/2, y−1/2, −z+1/2.

C–F···π and S–O···π interactions (Å,°) top

Cg1 and Cg3 are the centroids of the C9/N10/C11–C14 and C5–C8/C13/C14 rings, respectively.

X	I	J	I···J	X···J	X–I···J
C27	F30	Cg3^v	3.115 (3)	4.233 (3)	143.0 (2)
S23	O26	Cg1^v	3.085 (3)	4.167 (2)	131.4 (2)

Symmetry code: (v) –x + 3/2, y + 1/2, –z + 1/2.

π–π interactions (Å, °) top

Cg1 and Cg2 are the centroids of the C9/N10/C11–C14 and C1–C4/C11/C12 rings, respectively. CgI···CgJ is the distance between ring centroids. The dihedral angle is that between the planes of the rings I and J. CgI_Perp is the perpendicular distance of CgI from ring J. CgI_Offset is the distance between CgI and perpendicular projection of CgJ on ring I.

I	J	CgI···CgJ	Dihedral angle	CgI_Perp	CgI_Offset
1	2ⁱⁱⁱ	3.806 (2)	2.11 (15)	3.575 (2)	1.306 (2)
2	1ⁱⁱⁱ	3.806 (2)	2.11 (15)	3.530 (2)	1.423 (2)
2	2ⁱⁱⁱ	3.886 (2)	0.02 (15)	3.563 (2)	1.551 (2)

Symmetry code: (iii) –x + 2, –y + 1, –z + 1.

Acknowledgements

This study was financed by the State Funds for Scientific Research (grant DS No. 8220-4-0087-9).

References

Bianchi, R., Forni, A. & Pilati, T. (2004). Acta Cryst. B60, 559–568. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Dorn, T., Janiak, C. & Abu-Shandi, K. (2005). CrystEngComm, 7, 633–641. Web of Science CSD CrossRef CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Hunter, C. A., Lawson, K. R., Perkins, J. & Urch, C. J. (2001). J. Chem. Soc. Perkin Trans. 2, pp. 651–669. Web of Science CrossRef Google Scholar
Huntress, E. H. & Shaw, E. N. (1948). J. Org. Chem. 13, 674–675. CrossRef PubMed CAS Web of Science Google Scholar
King, D. W., Cooper, W. J., Rusak, S. A., Peake, B. M., Kiddle, J. J., O'Sullivan, D. W., Melamed, M. L., Morgan, C. R. & Theberge, S. M. (2007). Anal. Chem. 79, 4169–4176. Web of Science CrossRef PubMed CAS Google Scholar
Novoa, J. J., Mota, F. & D'Oria, E. (2006). Hydrogen Bonding – New Insights, edited by S. Grabowski, pp. 193–244. The Netherlands: Springer. Google Scholar
Oxford Diffraction (2008). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Yarnton, England. Google Scholar
Roda, A., Guardigli, M., Michelini, E., Mirasoli, M. & Pasini, P. (2003). Anal. Chem. A75, 462–470. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sikorski, A., Kowalska, K., Krzymiński, K. & Błażejowski, J. (2007). Acta Cryst. E63, o2670–o2672. Web of Science CSD CrossRef IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Takahashi, O., Kohno, Y., Iwasaki, S., Saito, K., Iwaoka, M., Tomada, S., Umezawa, Y., Tsuboyama, S. & Nishio, M. (2001). Bull. Chem. Soc. Jpn, 74, 2421–2430. Web of Science CrossRef CAS Google Scholar
Trzybiński, D., Krzymiński, K., Sikorski, A., Malecha, P. & Błażejowski, J. (2010). Acta Cryst. E66, o826–o827. Web of Science CrossRef IUCr Journals Google Scholar
Wróblewska, A., Huta, O. M., Midyanyj, S. V., Patsay, I. O., Rak, J. & Błażejowski, J. (2004). J. Org. Chem. 69, 1607–1614. Web of Science CrossRef PubMed CAS Google Scholar
Zomer, G. & Jacquemijns, M. (2001). Chemiluminescence in Analytical Chemistry, edited by A. M. Garcia-Campana & W. R. G. Baeyens, pp. 529–549. New York: Marcel Dekker. Google Scholar

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Volume 66| Part 7| July 2010| Pages o1548-o1549

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